• Bulletin of the Korean Chemical Society
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• 제30권9호
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• pp.1939-1945
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• 2009

Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

• 대한화학회지
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• 제30권2호
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• pp.145-151
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• 1986

3-CN, 4-CN, $3-NH_2$ 및 $4-NH_2$ 치환피리딘의 해리상수를 온도(15 ∼ 40${\circ}C$)와 압력(1-2500bar)을 변화시키면서 측정하였다. 측정방법은 전도도법을 적용했으나 낮은 해리상수를 가진 물질에서도 적용되는 피리딘류의 염용액의 전도도를 측정하므로 계산가능한 방법을 모색하여 응용하였다. 이 방법은 어떤 조건에서의 해리상수를 알고 있어야 하는 것과 실험값을 외삽하여 피리딘염의 전도도를 알아야 하는 번거로움도 있으나 측정이 가능하다는 것을 확인할 수 있다. 이들 치환체의 해리상수는 온도가 증가하면 커지고 압력이 높아지면 해리상수는 작아진다는 것을 알 수 있었다. 또 반응의 열역학적 성질을 계산하여 반응성도 고찰하였다.

• 한국재료학회지
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• 제21권8호
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• pp.439-443
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• 2011

The crystal structure and magnetic properties of a new solid solution type ferrite $(Fe_2O_3)_5-(Al_2O_3)_{3.4}-(Ga_2O_3)_{0.6}-SiO$ were investigated using X-ray diffraction and M$\"{o}$ssbauer spectroscopy. The results of the X-ray diffraction pattern indicated that the crystal structure of the sample appears to be a cubic spinel type structure. The lattice constant (a = 8.317 ${\AA}$) decreases slightly with the substitution of $Ga_2O_3$ even though the ionic radii of the Ga ions are larger than that of the Al ions. The results can be attributed to a higher degree of covalency in the Ga-O bonds than in the Al-O and Fe-O bonds, which can also be explained using the observed M$\"{o}$ssbauer parameters, which are the magnetic hyperfine field, isomer shift, and quadrupole splitting. The drastic change in the magnetic structure according to the Ga ion substitution in the $ (Fe_2O_3)_5(Al_2O_3)_{4-x}(Ga_2O_3)_xSiO$ system and the low temperature variation have been studied through a M$\"{o}$ssbauer spectroscopy. The M$\"{o}$ssbauer spectrum at room temperature shows the superpositions of two Zeeman patterns and a strong doublet. It shows significant departures from the prototypical ferrite and is comparable with the diluted ferrite. The doublet of spectrum at room temperature appears to originate from superparamagnetic clusters and also the asymmetry of the doublet appears to be caused by the preferred orientation of the crystallites. The M$\"{o}$ssbauer spectra below room temperature show various complicated patterns, which can be explained by the freezing of the superparamagnetic clusters. On cooling, the magnetic states of the sample were various and multi critical.

• The Korean Journal of Physiology
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• 제16권2호
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• pp.119-128
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• 1982

The frog truncus arterious were studied with conventional glass microelectrode technique in order to elucidate the underlying mechanism of spontaneous pacemaker activity. The analyses were focussed on the ionic nature of pacemaker current by changing the concentrations of extracellular $K^+$ and, $Na^+$, or by using blockers of K- and Ca-current and chronotropic transmitters. 1) The action potential of the spontaneously active truncus arteriosus has some characteristic feature of maximal distolic potential ranged from -65 to -75 mV, resting potential from -45 to -50 mV and overshoot voltage about +30 mV, respectively. Duration of the action potential taken from rapid upstroke to maximal diastolic potential was about 600 msec. Usual discharge rate was $25{\sim}30/min$ at room temperature $(18{\sim}20^{\circ}C)$. 2) The sensitivity of the resting membrane potential to change extracellular potassium concentrations $(0{\sim}12\;mM)$ was relatively low. Transient hyperpolarization was appeared in the 12 mM K Ringer after 10 min exposure to 0 mM K and it could be related to Na-pump reactivation by high potassium. 3) Reduction of extracellular sodium concetrations diminished the amplitude and frequency of the action potential. In Ringer solution containing 30% Na (substituted by equimolar Tris), spontaneous activity stopped but reappeared as very slow and small action potential. There was no spotaneous activity in zero Na Ringer solution. 4) Caesium(10 mM), K-current blocker decreased the frequency of the action potential and also pacemaker depolarization. Manganese (2 mM) known to be Ca-current antagonist, blocked spontaneous activity completely. 5) Adrenaline and acetylcholine had no chronotropic effect. But adrenaline increased the duration of plateau phase and the magnitude of the action potential in the follower cell. It is concluded that K-, Na-and Ca-current components are involved in the genesis of spontaneous activity of the frog truncus arteriosus like cardiac pacemaker tissues. But the insensitivity of truncus arteriosus to adrenaline and acetylcholine indicates that there are some different control mechanisms of spontaneous rhythm in two tissues.

• 한국재료학회지
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• 제11권3호
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• pp.203-206
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• 2001

SrTiO$_3$첨가량 및 소결온도에 따른 YIG 소결체의 미세구조 및 자기적 특성변화에 대하여 조사하였다. 소량의 SrTiO$_3$소결재를 첨가한 결과 소결체의 격자상수는 약간 증가하였으며, 이는 소결시 $Y^{+3}$, Fe$^{+3}$이온이 이온반경이 상대적으로 큰 Sr$^{+2}$, Ti$^{+4}$이온으로 치환되었기 때문인 것으로 추정된다. SrTiO$_3$소결재를 0.2mo1% 첨가하고, 142$0^{\circ}C$에서 소결한 소결체의 밀도는 이론밀도의 98%이상의 치밀화를 얻을 수 있었다. 상온에서의 포화자화값(M$_s$)은 SrTiO$_3$소결재의 첨가량이 증가함에 따라 약간 감소하였으나 큰 변화는 없었다. 더욱이 온도에 따른 보자력 (H$_c$)의 변화는 없었다.

• 한국세라믹학회지
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• 제53권5호
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• pp.500-505
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• 2016

Scandia-stabilized zirconia co-doped with $CeO_2$ is a promising electrolyte for intermediate temperature SOFC, but still shows rapid degradation during a long-term operation. In this study, $CeO_2$ (1 mol%) as a stabilizer is partially substituted with lanthanum oxides ($M_2O_3$, M=Yb, Gd, Sm) to stabilize a cubic phase and thus durability in reducing atmosphere. 0.5M0.5Ce10ScSZ electrolytes were prepared by solid state reaction and sintered at $1450^{\circ}C$ for 10 h to produce dense ceramic specimens. With addition of the lanthanum oxide, 0.5M0.5Ce10ScSZ showed lower degradation rates than 1Ce10ScSZ. Since $Gd_2O_3$ showed the highest ionic conductivity among the co-dopants, an electrolyte-supported cell with 0.5Gd0.5Ce10ScSZ was prepared to compare its long-term performance with that of 1Ce10ScSZ-based cell. Maximum power density of 0.5Gd0.5Ce10ScSZ-based cell was degraded by about 2.3% after 250 h, which was much lower than 1Ce10ScSZ-based cell (4.2%).

• Korean Chemical Engineering Research
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• 제59권4호
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• pp.557-564
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• 2021

페로브스카이트 구조를 갖는 Sr_0.92Y_0.08Ti_1-xV_xO_3-δ (SYTV)는 고체산화물 연료 전지(Solid oxide fuel cell, SOFC)에서 H₂S를 포함하는 연료를 사용하기 위한 대체 연료극으로 연구되었다. Sr_0.92Y_0.08TiO_3-δ (SYT)의 전기화학적 성능을 향상시키기 위해 페로브스카이트의 B-사이트에 위치한 티타늄을 바나듐으로 치환하였다. 페치니법을 통해 합성된 SYTV는 작동 온도 조건에서 추가적인 부산물의 형성 없이 YSZ(yttria-stabilized zirconia) 전해질과 화학적으로 안정했다. 바나듐의 치환량이 증가함에 따라 산소 공공 결함(Oxygen vacancy)이 증가하였으며, 생성된 산소 공공 결함으로 인해 연료극의 이온 전도도가 증가했다. 전지 성능은 850 ℃ 순수한 H₂ 연료 조건에서 바나듐 치환 정도에 따라 1 mol.%의 바나듐이 치환된 경우 19.30 mW/cm² 이고 7 mol.%의 바나듐이 치환된 경우 34.87 mW/cm²이다. 1000 ppm의 H₂S를 포함하는 H₂ 연료조건에서 cell의 최대 전력밀도는 1 mol.%의 경우 22.34 mW/cm²이고 7 mol.%의 경우 73.11 mW/cm²로 증가하였다.

• 전기화학회지
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• 제15권2호
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• pp.95-100
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• 2012

올리빈 구조를 가지는 $LiFePO_4$ 양극활물질은 낮은 가격과 안정성으로 인해 리튬 이차전지 시장에서 큰 관심을 받고 있다. 그러나 낮은 이온 전도도와 작동전압 때문에 상업적으로 이용되기엔 사용분야의 응용에 제한이 있다. 이러한 문제를 해결하기 위해서 철 양이온을 망간 양이온과 같은 전이금속으로 치환함으로써 작동전압을 높이는 연구가 시행되고 있다. 또한 미세구조의 나노화를 통해 리튬 이온의 확산거리를 짧게 만들어 줌으로써 이온 전도도를 높여주는 연구도 진행 중이다. 그래서 이번 연구에서는 이온의 확산거리를 짧게 만들어 주기 위해 표면적을 넓힐 수 있는 전기방사를 이용해 물질을 합성하였고, 이를 확인하기 위하여 시차주사현미경 관측을 통해 균일한 나노 섬유의 형성을 확인하였다. 또한 결정구조를 관찰하기 위해 X-선 회절 분석을 하였는데, 다른 상의 관찰 없이 단일상의 결정구조를 얻음을 확인하였다. 전기화학적 성능 확인방법으로는 충방전 테스트기를 이용하여 초기 충방전 곡선을 분석하였고, 계면저항 및 리튬 양이온의 확산을 알아보기 위해 임피던스 측정을 실행하였다.

• 한국응용과학기술학회지
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• 제7권1호
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• 공업화학
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• 제9권5호
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• pp.774-780
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• 1998

스피넬 구조인 $LiMn_2O_4$의 안정성을 향상시키기 위해서 망간과 비슷한 이온반경을 갖는 여러 가지 금속원소, Mg, Fe, V, W, Cr, Mo들을 일부 치환하였으며 ($LiM_xMn_{2-x}O_4(0.05{\leq}x{\leq}0.02)$), 이 결과 $LiM_xMn_{2-x}O_4$ 정극은 정극물질로 사용할 경우 $LiMn_2O_4$보다 낮은 용량감소를 나타냈다. 그리고 화학확산계수의 측정 결과 $LiMg_{0.05}Mn_{1.9}O_4$와 $LiCr_{0.1}Mn_{1.9}O_4$의 화학확산계수는 $LiMn_2O_4$보다 약 10배 이상 크게 나타났다. 이러한 결과를 볼 때 $LiMn_2O_4$에 여러 가지 금속원소를 치환시킴으로 구조적인 안정화로 인한 전기화학적 성능을 향상시킬 수 있었다.